CN116477645A - Low-cost simplified process for preparing high-purity cesium salt and high-purity rubidium salt products - Google Patents
Low-cost simplified process for preparing high-purity cesium salt and high-purity rubidium salt products Download PDFInfo
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 150000003297 rubidium Chemical class 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 156
- 238000000605 extraction Methods 0.000 claims abstract description 124
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 83
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 67
- FAWNVSNJFDIJRM-UHFFFAOYSA-N [Rb].[Cs] Chemical compound [Rb].[Cs] FAWNVSNJFDIJRM-UHFFFAOYSA-N 0.000 claims abstract description 59
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 51
- 239000011591 potassium Substances 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 238000001914 filtration Methods 0.000 claims abstract description 41
- 239000012074 organic phase Substances 0.000 claims abstract description 38
- 239000012266 salt solution Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 24
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229940037003 alum Drugs 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 12
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 12
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 12
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 12
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 235000002906 tartaric acid Nutrition 0.000 claims description 11
- 239000011975 tartaric acid Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 10
- 239000001472 potassium tartrate Substances 0.000 claims description 10
- 229940111695 potassium tartrate Drugs 0.000 claims description 10
- 235000011005 potassium tartrates Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 13
- 238000001953 recrystallisation Methods 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 159000000006 cesium salts Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001471 micro-filtration Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 159000000005 rubidium salts Chemical class 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- -1 biochemistry Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- HEQUOWMMDQTGCX-UHFFFAOYSA-L dicesium;oxalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C([O-])=O HEQUOWMMDQTGCX-UHFFFAOYSA-L 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- DUXDETQJUQZYEX-UHFFFAOYSA-L oxalate;rubidium(1+) Chemical compound [Rb+].[Rb+].[O-]C(=O)C([O-])=O DUXDETQJUQZYEX-UHFFFAOYSA-L 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- KDKJYYNXYAZPIK-UHFFFAOYSA-J aluminum potassium disulfate hydrate Chemical compound O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KDKJYYNXYAZPIK-UHFFFAOYSA-J 0.000 description 1
- VHUJINUACVEASK-UHFFFAOYSA-J aluminum;cesium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Cs+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VHUJINUACVEASK-UHFFFAOYSA-J 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009993 causticizing Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910001744 pollucite Inorganic materials 0.000 description 1
- ZDCPCNYMFTYBBX-UHFFFAOYSA-N potassium rubidium Chemical compound [K].[Rb] ZDCPCNYMFTYBBX-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a low-cost simplified process for preparing two products of high-purity cesium salt and high-purity rubidium salt, which comprises the following steps: s1, removing potassium and aluminum from a mixed solution containing rubidium, cesium and potassium to obtain a purified rubidium cesium salt solution; s2, cesium extraction is carried out on the purified rubidium cesium salt solution to obtain a cesium extraction organic phase and a cesium extraction residual liquid; extracting cesium in an organic reverse way to obtain cesium back-extraction liquid; precisely filtering cesium back-extraction liquid, sequentially evaporating, concentrating, crystallizing, drying, calcining, recrystallizing and drying to obtain high-purity cesium salt; s3, introducing high-purity CO into the cesium extraction raffinate 2 Filtering until the pH value is not changed, and obtaining rubidium carbonized liquid and carbonate impurity salt precipitate; and (3) performing precise filtration, evaporation concentration crystallization, drying calcination, recrystallization and drying on the rubidium carbide liquid to obtain the high-purity rubidium carbonate. The invention omits the processes of extracting rubidium from cesium extraction residual liquid and back extracting rubidium, simplifies the process, and achieves the purposes of greatly reducing the process period, equipment and reagent cost and improving the production efficiency.
Description
Technical Field
The invention belongs to the technical field of alkali metal element extraction, and particularly relates to a low-cost simplified process for preparing two products of high-purity cesium salt and high-purity rubidium salt.
Background
Rubidium cesium has unique properties, so that the rubidium cesium has important application in a plurality of fields, not only has a plurality of traditional application fields, but also has new application fields, and particularly in a plurality of high-tech fields, rubidium cesium has an increasingly important effect. Rubidium and cesium have been greatly developed in recent 10 years in the traditional application fields of electronic devices, catalysts, special glass, biochemistry, medicine and the like; in the new application fields of magnetohydrodynamic power generation, thermoionic conversion power generation, ion propulsion engine, laser energy conversion electric energy device, cesium ion cloud communication and the like, rubidium and cesium also show strong vitality. At present, the main raw materials for the industrial production of rubidium and cesium salts in the world are pollucite and lepidolite. Rubidium and cesium are active in nature, and are extremely prone to losing outer electrons, and exist in a solution in the form of soluble salts. Rubidium and cesium reserves in nature are rich, but the content is low, and the rubidium and cesium are often symbiotic with other alkali metals such as lithium, sodium and potassium. In the prior art, the extraction method of rubidium and cesium comprises a precipitation method, an ion exchange method, an extraction method and the like.
Chinese application CN115725855a discloses a method for preparing high-purity cesium salt and high-purity rubidium salt, wherein tartaric acid is added into potassium-containing rubidium cesium alum solution to make potassium and tartaric acid generate potassium tartrate, and cooling recrystallization is performed to precipitate rubidium cesium alum in a crystal form to obtain potassium-removed rubidium cesium alum crystal. Dissolving rubidium cesium alum crystals in water again, precipitating aluminum by adopting an aluminum removing agent to obtain purified cesium rubidium salt solution, carrying out cesium extraction on the purified cesium rubidium salt solution to obtain cesium extraction organic phase and cesium extraction residual water, and carrying out back extraction on the cesium extraction organic phase by taking ammonium salt or acid as a back extractant to obtain cesium back extraction liquid. Adding alkali into the cesium extraction residual water to adjust the pH value, adding an extractant to obtain a rubidium extraction organic phase, and carrying out reverse extraction on the rubidium extraction organic phase by using a reverse extractant to obtain rubidium reverse extraction liquid. And finally, respectively carrying out precise filtration on the cesium strip liquor and the rubidium strip liquor, and sequentially carrying out evaporation concentration, drying, calcination, redissolution and drying to obtain high-purity cesium salt and high-purity rubidium salt. Wherein the extractant used for cesium extraction and rubidium extraction is a mixture of t-BAMBP, diethylbenzene and kerosene. In another example, CN104016384a discloses a method for preparing high-purity cesium carbonate and high-purity rubidium carbonate, which comprises separating cesium by using t-BAMBP as extractant and sulfonated kerosene and diethylbenzene as diluents, preparing back-extraction acid with high-purity oxalic acid, and extracting cesium by back-extraction to obtain cesium oxalate; then, t-BAMBP is used as an extractant, sulfonated kerosene and dimethylbenzene are used as diluents to extract and separate rubidium from cesium raffinate, and high-purity oxalic acid is used for preparing back-extraction acid to carry out organic extraction on rubidium to carry out back-extraction on rubidium, so that rubidium oxalate is obtained; crystallizing by recrystallization equipment to obtain cesium oxalate and rubidium oxalate crystals, and calcining to obtain high-purity cesium carbonate and high-purity rubidium carbonate.
In the above processes, the cesium raffinate is extracted by using an organic phase containing t-BAMBP to obtain a rubidium extracted organic phase, and the organic phase is back extracted by using acid, and then subjected to precise filtration and recrystallization to obtain the high-purity rubidium salt. The organic phase containing t-BAMBP is used for extracting cesium and rubidium sequentially, the consumption of an extracting agent is high, and t-BAMBP is expensive, about 30 ten thousand/t, so that the process cost is high. In addition, the rubidium extraction process of cesium raffinate needs to be provided with a special pH adjusting stirring tank and a 12-level or so centrifugal extractor, and the equipment cost is high. For the above reasons, improvements in the existing processes for preparing high purity cesium salts and rubidium salts are needed.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and disadvantages of the prior art, the present invention provides a low-cost simplified process for preparing two products of high-purity cesium salt and high-purity rubidium salt, which simplifies the existing process for preparing high-purity cesium salt and high-purity rubidium salt, thereby achieving the purpose of greatly reducing reagent cost and equipment cost, shortening working procedures, and improving production efficiency.
(II) technical scheme
A low cost simplified process for preparing both high purity cesium salt and high purity rubidium salt products comprising:
s1, removing potassium and aluminum from a mixed solution containing rubidium, cesium and potassium to obtain a purified rubidium cesium salt solution;
s2, cesium extraction is carried out on the purified rubidium cesium salt solution to obtain a cesium extraction organic phase and a cesium extraction residual liquid; washing the cesium extraction organic phase; back-extracting the washed cesium extraction organic phase by using a back-extracting agent to obtain cesium back-extracting solution; precisely filtering cesium back-extraction liquid, sequentially evaporating, concentrating, crystallizing, drying, calcining, recrystallizing and drying to obtain high-purity cesium salt;
s3, introducing high-purity CO into the cesium extraction raffinate 2 Until the pH value is not changed (generally reaching 8-9), filtering to obtain rubidium carbide liquid and carbonate impurity salt precipitate; and precisely filtering the rubidium carbide liquid, evaporating, concentrating, crystallizing, drying, calcining, recrystallizing and drying to obtain the high-purity rubidium carbonate.
According to a preferred embodiment of the present invention, in S1, the mixed solution containing rubidium, cesium and potassium is obtained by dissolving mixed alum containing rubidium, cesium and potassium in deionized water.
The mixed solution containing rubidium, cesium and potassium can be prepared from acidic mixed alum and alkaline mixed salt, and the mixed solution can be an acidic solution or an alkaline solution. The acidic mixed alum is the most ideal raw material, and can be directly treated by removing potassium and aluminum, and other raw materials are required to be added with reagents to be converted into alum and then treated according to the process of the invention. However, the raw materials suitable for the process of the invention are any rubidium and cesium containing raw materials, and no matter the content of potassium and sodium, two products of cesium salt and rubidium salt with the purity of more than 99.9% can be obtained as long as the products can be converted into alum through the reaction of the reagent and then treated according to the process of the invention. For some cesium-containing rubidium-potassium raw materials which are not alum, the raw materials are firstly converted into alum by adding a reagent, purified cesium-rubidium alum is obtained by recrystallization, and then the process is operated according to the invention.
According to a preferred embodiment of the present invention, in S1, the potassium removing method includes: adding tartaric acid into the mixed solution containing rubidium, cesium and potassium, wherein the molar ratio of the tartaric acid to potassium in the mixed solution containing rubidium, cesium and potassium is 0.2-0.7, heating to 50-95 ℃, reacting for 1-3h, standing for 12-24h, cooling, recrystallizing, centrifugally separating to separate rubidium salt and cesium salt in a crystal form, and keeping potassium tartrate in the solution to obtain a potassium tartrate solution and rubidium cesium salt crystals with potassium content lower than 0.0035%. And (5) recycling the potassium tartrate solution.
According to a preferred embodiment of the present invention, in S1, the aluminum removal method includes: dissolving rubidium cesium salt crystals in deionized water, adding barium hydroxide solution or calcium hydroxide solution, heating and stirring to react while controlling the pH at the reaction end point to be 6.5-8.5, and preserving heat for 10-60min after reaching the reaction end point to precipitate aluminum in the form of aluminum hydroxide; centrifugally separating the reaction mixture to obtain clear liquid and precipitate slag; and (3) performing precise filtration on the clear liquid to obtain purified rubidium cesium salt solution and filter residues.
Wherein the barium hydroxide solution or the calcium hydroxide solution is prepared by dissolving analytically pure barium hydroxide or analytically pure calcium oxide in deionized water.
According to the preferred embodiment of the invention, in S2, before cesium extraction, the pH value of the purified rubidium cesium salt solution is adjusted to be alkaline, and the purified rubidium cesium salt solution and filter residues are obtained through precise filtration; cesium extraction is carried out on the causticized and purified cesium rubidium salt solution.
Preferably, before cesium extraction, adding calcium hydroxide or barium hydroxide solution into the purified rubidium cesium salt solution, heating and stirring for reaction at 90-97 ℃, controlling the pH at the reaction end point to be more than or equal to 13.0, and preserving heat for 10-60min after reaching the reaction end point to enable cesium to be completely dissolved in a water phase in the form of cesium hydroxide; precisely filtering to obtain causticized purified cesium rubidium salt solution and barium slag or calcium slag; cesium extraction is carried out on the causticized and purified cesium rubidium salt solution.
According to a preferred embodiment of the present invention, in S2, the cesium extraction method comprises: taking a mixed solvent of t-BAMBP, diethylbenzene and kerosene as an extracting agent, and carrying out cesium extraction on the causticized and purified cesium rubidium salt solution to obtain a cesium extraction organic phase and a cesium extraction residual liquid; washing the cesium extraction organic phase by using water or dilute alkali aqueous solution as a detergent to obtain a washing solution and a cesium extraction organic phase after washing; and (3) after washing, back-extracting the cesium extraction organic phase by taking ammonium carbonate or oxalic acid as a back-extracting agent to obtain cesium back-extracting solution. And (3) carrying out fine filtration on the cesium back-extraction solution, sequentially carrying out evaporation concentration crystallization, drying calcination, recrystallization and drying to obtain the high-purity cesium carbonate. If sulfuric acid or nitric acid or the like is used as a stripping agent, the product is the corresponding cesium sulfate or cesium nitrate.
According to the preferred embodiment of the invention, step S1 is carried out, wherein the removal rate of potassium and aluminum in the mixed solution containing rubidium, cesium and potassium reaches more than 99.9%; after the treatment of the step S2, the cesium removal rate in the purified rubidium cesium salt solution reaches more than 99.9 percent.
According to a preferred embodiment of the present invention, in step S3, the solubles in the cesium raffinate are RbOH, and the remaining impurities are mainly trace Ba, fe, ca, mg metal ions; introducing high-purity carbon dioxide gas to enable impurity metal ions to generate carbonate precipitates, and performing precise filtration to obtain purified rubidium carbide liquid; evaporating, concentrating, crystallizing, drying, calcining, redissolving in deionized water, evaporating, concentrating, crystallizing again, and drying to obtain high-purity rubidium carbonate.
In step S3, high-purity CO is introduced into the cesium extraction raffinate 2 The pH is brought to a value of 8 to 9, preferably pH8.5.
Preferably, the microfiltration in the above step is a microfiltration of 0.08 to 0.15 μm.
(III) beneficial effects
Compared with the prior art, the invention omits the process of extracting rubidium from cesium extraction residual liquid by using an organic phase extractant containing t-BAMBP, directly introduces high-purity carbon dioxide into the cesium extraction residual liquid to carbonize to generate rubidium carbide liquid (a mixture composed of rubidium carbonate and rubidium bicarbonate), the rubidium carbonate and the rubidium bicarbonate are soluble in water, and trace metal impurities such as calcium, magnesium, barium and iron (generally impurities contained in cesium-rubidium mixed alum or a small amount of impurities introduced in the aluminum removal process) in the cesium extraction residual liquid are carbonized to generate carbonate insoluble particles, and after precise filtration, filtrate is the high-purity rubidium carbide liquid, and is subjected to evaporation concentration crystallization, drying calcination, recrystallization and drying to obtain the high-purity rubidium carbonate. By omitting the operation of extracting rubidium from the cesium extraction raffinate, the following technical effects can be achieved:
(1) The process period is shortened, the equipment cost is lower, the reagent cost is less, and the pollution is smaller; the method specifically comprises the following steps:
(1) when rubidium extraction is carried out on the cesium extraction raffinate by the original process, the pH value is more than or equal to 13.0 by using strong alkali, an extractant (t-BAMBP+sulfonated kerosene+diethylbenzene/xylene) and a back extractant are prepared, the extraction phase and the extraction time are controlled, and after improvement, only the carbonization endpoint (pH value of 8-9) of the cesium extraction raffinate is controlled, thereby reducing the rubidium extraction and back extraction processes and time consumption and greatly shortening the process cycle. The actual running condition estimates that the carbonization process can be completed within 1h, and the original process comprises four main processes of regulating the pH value of cesium extraction raffinate to regenerating lean organic phase and preparing back extraction agent and regenerating agent for at least 10h. The quality and parameter stability of the intermediate product are monitored in each working procedure, and the product analysis detection and the equipment operation parameter adjustment are carried out at regular time in the process. Compared with the prior art, the invention greatly reduces the process period, the labor cost, the reagent cost, the management cost and the like.
(2) The rubidium extraction procedure of the original technology needs a pH stirring tank, a 15-level left and right centrifugal extractor and a filter device, the pH stirring tank and the precise filter device are put into about 1 ten thousand yuan, one centrifugal extractor is about 10 ten thousand yuan, and 15-level extraction (8-level rubidium extraction, 4-level back extraction and 3-level regeneration) needs about 150 ten thousand yuan, which is 151 ten thousand yuan; only one PP carbonization tower and precise filtering equipment are needed after improvement, and the equipment cost investment is not more than 1 ten thousand yuan; the cost of the improved equipment for preparing the high-purity rubidium salt is 1/151 of that of the original technology, the equipment quantity and the occupied area are only 1/15 of that of the original technology, and the investment cost of the equipment and the factory building is greatly reduced.
(3) The prior art needs t-BAMBP for rubidium extraction, wherein t-BAMBP is a well known special rubidium cesium extractant in industry, the price is high, about 30 ten thousand/t, and in addition, the rubidium back extraction also needs pure water of a back extractant, a regenerant and a matched reagent; and the improved process only needs high-purity carbon dioxide gas, so that the reagent input cost is greatly reduced.
(4) The original technology is subjected to rubidium extraction and back extraction, so that a large amount of rubidium raffinate (rubidium-lean organic phase) is generated, and the part contains a small amount of t-BAMBP, diethylbenzene (or dimethylbenzene) and kerosene which need to be purified; meanwhile, a small amount of organic phase is mixed in the rubidium stripping solution, and purification is also needed; and the improved process directly introduces high-purity carbon dioxide gas into cesium extraction raffinate, so that three wastes are not generated. The improved process has obvious environmental protection advantage, and simultaneously saves the investment of environmental protection equipment.
(5) The original process is provided with 3 to 4 people because of the long flow, more equipment, reagent configuration and product monitoring analysis, and the simplified process only needs 1 person, so that the labor cost is greatly reduced. If automation is to be realized in the original process, the cost of the whole process for installing the automatic control device is far higher than that of the process provided by the invention.
(2) The yield of the high-purity rubidium carbonate product is compared with that of the original process: the process is simplified without the step of regulating the pH value by using strong alkali, rubidium is not carried away by slag, and the yield can be improved by more than 2.5 percent according to the calculation of the experimental actual yield.
(3) The purity of the high-purity rubidium carbonate product is compared with that of the original process: the impurity indexes of calcium, magnesium, lithium and the like are superior to those of the extraction process, and the potassium and sodium indexes are lower than those of the extraction process, but all reach more than 99.9 percent of standards.
In summary, although the process of extracting rubidium and back extracting rubidium from cesium extraction raffinate by using t-BAMBP and the like is omitted compared with the prior art, the purity and the yield of the high-purity rubidium carbonate product are not reduced compared with the prior art, so that the simplified process can obtain two products of high-purity cesium salt and high-purity rubidium salt, the purity and the yield of the products are not lower than those of the prior art, and meanwhile, the simplified process has remarkable advantages in terms of process cycle, equipment cost, reagent cost, environmental protection, labor and the like.
Drawings
FIG. 1 is a simplified process diagram of the present invention for preparing two products, a high purity cesium salt and a high purity rubidium salt, at low cost.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
As shown in figure 1, the invention provides a low-cost simplified process for preparing two products of high-purity cesium salt and high-purity rubidium salt, which mainly comprises the steps of introducing high-purity CO into cesium extraction raffinate 2 Stabilizing pH, and filtering to obtain rubidium carbide liquid and carbonate impurity salt (carbonate of calcium, magnesium, barium and iron, etc.) precipitate; and precisely filtering the rubidium carbide liquid, evaporating, concentrating, crystallizing, drying, calcining, recrystallizing and drying to obtain the high-purity rubidium carbonate. The invention uses the method of directly carbonizing the cesium extraction raffinate to replace the prior art that caustic alkali is used for adjusting the pH to be more than or equal to 13, t-BAMBP extractant is used for extraction, ammonium salt or acid is used as a back extractant for back extractionTaking and the like.
As shown in fig. 1, the overall process of the low-cost simplified process for preparing both high-purity cesium salt and high-purity rubidium salt products comprises:
step 1: and dissolving the mixed alum containing rubidium, cesium and potassium in deionized water to obtain a mixed solution containing rubidium, cesium and potassium. For some materials containing cesium, rubidium and potassium and not in the form of alum, the materials are converted into alum by adding reagents, and then the alum is purified by recrystallization, and the high-purity cesium salt and the high-purity rubidium carbonate salt with the purity of more than 99.9% can be prepared according to the process operation of the invention.
Step 2: and (5) removing potassium from the mixed solution.
The potassium removing method comprises the following steps: adding tartaric acid into a mixed solution containing rubidium, cesium and potassium, wherein the molar ratio of the tartaric acid to the potassium in the mixed solution containing rubidium, cesium and potassium is 0.2-0.7, heating to 50-95 ℃, reacting for 1-3h, standing for 12-24h, cooling and recrystallizing to precipitate rubidium and cesium salt in the form of rubidium cesium salt crystals, and retaining potassium tartrate in the solution to obtain a potassium tartrate solution and rubidium cesium salt crystals with potassium content lower than 0.0035%. And (5) recycling the potassium tartrate solution.
By the potassium removal treatment, the removal rate of potassium in the rubidium cesium salt crystal salt reaches 99.9 percent.
Step 3: the mixed solution is subjected to aluminum removal.
Dissolving rubidium cesium salt crystals in deionized water, adding barium hydroxide solution or calcium hydroxide solution, heating and stirring to react while controlling the pH at the reaction end point to be 6.5-8.5, and preserving heat for 10-60min after reaching the reaction end point to precipitate aluminum in the form of aluminum hydroxide; centrifugally separating the reaction mixture to obtain clear liquid and precipitate slag; and (3) performing precise filtration on the clear liquid to obtain purified rubidium cesium salt solution and filter residues.
Centrifuging the reaction mixture to remove floccules with larger particle size formed by aggregating floccule aluminum hydroxide with calcium sulfate and/or barium sulfate, wherein the centrifugally separated precipitate has low water content and only very trace amount of rubidium and cesium is entrained, so that higher yield of rubidium and cesium can be ensured. The clear liquid also contains dispersed aluminum hydroxide suspended particles with small particle size, then the clear liquid is filtered by adopting precise filtration, so as to achieve the purpose of secondary aluminum removal (the secondary aluminum removal mainly comprises the removal of aluminum hydroxide suspended particles with small particle size, and the like, and also can remove calcium sulfate and/or barium sulfate with small particle size), and the obtained filtrate is qualified impurity removal liquid, wherein the content of aluminum ions is reduced to below 0.002g/L.
Wherein the barium hydroxide solution or the calcium hydroxide solution is prepared by dissolving analytically pure barium hydroxide or analytically pure calcium oxide in deionized water.
Through the aluminum removal treatment, the removal rate of aluminum in the mixed solution reaches 99.9 percent.
Step 4: causticizing and cesium extraction.
(1) Adding calcium hydroxide or barium hydroxide solution into the purified rubidium cesium salt solution, heating and stirring for reaction at 90-97 ℃, controlling the pH at the reaction end point to be more than or equal to 13.0, and preserving the temperature for 10-60min after reaching the reaction end point to ensure that cesium is completely dissolved in the water phase in the form of cesium hydroxide; precisely filtering to obtain causticized purified cesium rubidium salt solution and barium slag or calcium slag; cesium extraction is carried out on the causticized and purified cesium rubidium salt solution.
(2) Cesium extraction, the cesium extraction method is as follows: taking a mixed solvent of t-BAMBP, diethylbenzene and kerosene as an extracting agent, and carrying out cesium extraction on the causticized and purified cesium rubidium salt solution to obtain a cesium extraction organic phase and a cesium extraction residual liquid; washing the cesium extraction organic phase by using water or dilute alkali solution (such as ammonia water) as a detergent to obtain washing solution and a cesium extraction organic phase after washing; and (3) after washing, back-extracting the cesium extraction organic phase by taking ammonium carbonate or oxalic acid as a back-extracting agent to obtain cesium back-extracting solution. And (3) performing precise filtration on the cesium back-extraction solution, sequentially performing evaporation concentration crystallization, drying calcination, recrystallization and drying to obtain the high-purity cesium carbonate. If sulfuric acid or nitric acid or the like is used as a stripping agent to strip the cesium extraction organic phase, the final product is cesium sulfate or cesium nitrate. The ammonia water washing can not introduce metal ion impurities, and the washing effect is good.
Through the cesium extraction process, the cesium removal rate in the purified rubidium cesium salt solution reaches more than 99.9 percent.
Step 5: carbonizing the cesium extraction raffinate and refining to obtain high-purity rubidium carbonate.
The solubles in the cesium raffinate areRbOH, the rest impurities are mainly trace Ba, fe, ca, mg metal ions. The specific method comprises the following steps: directly introducing high-purity CO into cesium extraction raffinate 2 The pH value is not changed (usually 8-9), and the rubidium carbide liquid and carbonate impurity salt (calcium, iron, magnesium, barium and the like) precipitate are obtained through filtration; and precisely filtering the rubidium carbide liquid, evaporating, concentrating, crystallizing, drying, calcining, recrystallizing and drying to obtain the high-purity rubidium carbonate.
The fine filtration in each of the above steps is a fine filtration of 0.08 to 0.15. Mu.m, preferably a fine filtration of 0.10. Mu.m.
The features and effects of the present invention will be described in conjunction with the preferred embodiments of the present invention.
Example 1
The present example provides a simplified process for preparing high purity cesium salts and high purity rubidium salts, comprising the steps of:
(1): and (3) mixing and dissolving 300g of potassium, rubidium and cesium mixed alum and deionized water in a mass ratio of 1:4, heating to 75 ℃, and continuously stirring in the heating process to completely dissolve the rubidium and cesium alum, so as to obtain a mixed solution containing potassium, rubidium and cesium.
(2): tartaric acid is added into the mixed solution containing potassium, rubidium and cesium, the molar ratio of the added tartaric acid to potassium in the mixed solution containing potassium, rubidium and cesium is controlled to be 0.35, the mixed solution is heated to 60 ℃, and is continuously stirred in the heating process, so that the tartaric acid is dissolved and reacts for 2 hours, then the mixed solution is stood for 18 hours, cooled to room temperature and recrystallized, and centrifugal separation is carried out, so that rubidium-cesium-alum crystals and potassium tartrate solution are obtained. The potassium content in rubidium cesium alum crystals is not more than 0.0030 percent.
(3): dissolving rubidium cesium alum crystals in deionized water, slowly adding 1mol/L barium hydroxide solution, reaching the reaction end point when the pH value reaches 7.2, and continuously stirring for 0.5h to generate aluminum hydroxide and barium sulfate. And centrifugally separating the generated mixture to obtain precipitate slag and clear liquid. Filtering the clear solution by a microfiltration membrane with the diameter of 0.1 mu m to obtain purified cesium rubidium salt solution and barium slag precipitate. The aluminum content in the purified cesium rubidium salt solution is reduced to 0.002g/L.
Wherein, the aluminum hydroxide floccules are adsorbed and aggregated into large particles by barium residues, and the large particles are centrifugally separated; the water content of the centrifugated sediment is low, and only very trace amount of rubidium and cesium is entrained, so that the higher yield of rubidium and cesium can be ensured. The clear liquid also contains dispersed aluminum hydroxide suspended particles with small particle size, and then the clear liquid is filtered by adopting precise filtration, so that the aim of secondary aluminum removal is fulfilled.
(4): adding 1mol/L barium hydroxide solution into the purified cesium rubidium salt solution, regulating the pH value of the purified cesium rubidium salt solution to 13.2, and performing centrifugal separation to obtain causticized purified cesium rubidium salt solution and barium residues. And (3) taking a mixed solvent of t-BAMBP, diethylbenzene and kerosene as an extracting agent, and carrying out cesium extraction on the causticized and purified cesium rubidium salt solution to obtain a cesium extraction organic phase and cesium extraction residual water, wherein the cesium content in the cesium extraction residual water is reduced to 0.001g/L. And (3) washing the cesium extraction organic phase by taking ammonia water as a detergent to obtain a washing liquid and a cesium extraction organic phase after washing. And then back-extracting the cesium organic phase after washing by taking ammonium carbonate as a back-extracting agent to obtain cesium back-extracting solution and a lean organic phase. Rb/Cs in cesium strip liquor is less than 0.002.
(5): directly introducing high-purity CO into cesium extraction raffinate 2 And (3) leading the pH value to be 8 as a carbonization end point, and filtering to obtain rubidium carbonized liquid and carbonate impurity salt (calcium, iron, magnesium, barium and the like) precipitate.
(6): and respectively carrying out precise filtration on cesium back-extraction liquid and rubidium carbide liquid by using a microfiltration membrane with the diameter of 0.1 mu m, evaporating, concentrating and crystallizing the filtered solution, drying, calcining, re-dissolving in deionized water, recrystallizing and drying to obtain two products of high-purity cesium carbonate and high-purity rubidium carbonate.
Wherein, the purity of the high-purity cesium carbonate is 99.9 percent, and the yield is 88.13 percent; the purity of the high-purity rubidium carbonate is 99.9%, the yield is 92.69%, and the impurity metal ion content is as follows: cesium 0.003%, sodium 0.00012%, potassium 0.0012%, iron 0.0002%, aluminum 0.0002%, calcium 0.003%. According to the industry standard YS/T789-2012 of rubidium carbonate and the industry standard YS/T756-2011 of cesium carbonate, the purity and impurity metal ion content of the cesium carbonate and rubidium carbonate products prepared by the embodiment meet the industry standard.
The comparison of the embodiment with the prior art is as follows: in the case of preparing high purity rubidium salt, the equipment cost used in this example is 1/150 of that of the prior art, and the reagent cost is 2/5 (CO 2 Low cost), no wastewater treatment cost, and the process period is shortened to 1/10 of the prior process; the embodiment does not need innocent treatment of the lean organic phase after back extraction of rubidium, and three wastes are not generated. Meanwhile, the purity and recovery rate of the rubidium carbonate product prepared by the simplified process are not reduced.
Example 2
This example provides a simplified process for preparing high purity cesium salts and high purity rubidium salts, all of which are the same as in example 1, except for step (5). Directly introducing high-purity CO into cesium raffinate in step (5) 2 And (3) leading the pH value to be 9 as a carbonization end point, and filtering to obtain rubidium carbonized liquid and carbonate impurity salt (calcium, iron, magnesium, barium and the like) precipitate.
The purity of the final high-purity cesium carbonate is 99.9%, and the yield is 87.91%; the purity of the high-purity rubidium carbonate is 99.9%, the yield is 92.05%, and the impurity metal ion content is as follows: cesium 0.003%, sodium 0.00018%, potassium 0.0014%, iron 0.0002%, aluminum 0.00022%, calcium 0.0029%. According to the industry standard YS/T789-2012 of rubidium carbonate and the industry standard YS/T756-2011 of cesium carbonate, the purity and impurity metal ion content of the cesium carbonate and rubidium carbonate products prepared by the embodiment meet the industry standard.
In summary, the invention adopts the method of directly introducing high-purity carbon dioxide into cesium raffinate and controlling carbonization end point, and only improves the method for extracting rubidium from cesium raffinate and simultaneously maintains the cesium extraction and cesium back extraction process for the cesium rubidium mixed solution with potassium and aluminum removed, thereby greatly reducing the production cost and obtaining two high-purity products, shortening the process cycle, and creating considerable economic benefits for rubidium salt and cesium salt production enterprises for special enterprises producing cesium salt and rubidium salt. Economic benefits are the most major technical contribution brought by the invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A low cost simplified process for preparing both high purity cesium salt and high purity rubidium salt products comprising:
s1, removing potassium and aluminum from a mixed solution containing rubidium, cesium and potassium to obtain a purified rubidium cesium salt solution;
s2, cesium extraction is carried out on the purified rubidium cesium salt solution to obtain a cesium extraction organic phase and a cesium extraction residual liquid; washing the cesium extraction organic phase; back-extracting the washed cesium extraction organic phase by using a back-extracting agent to obtain cesium back-extracting solution; precisely filtering cesium back-extraction liquid, sequentially evaporating, concentrating, crystallizing, drying, calcining, recrystallizing and drying to obtain high-purity cesium salt;
s3, introducing high-purity CO into the cesium extraction raffinate 2 Filtering until the pH value is not changed, and obtaining rubidium carbonized liquid and carbonate impurity salt precipitate; and precisely filtering the rubidium carbide liquid, evaporating, concentrating, crystallizing, drying, calcining, recrystallizing and drying to obtain the high-purity rubidium carbonate.
2. The simplified low cost process of claim 1 wherein in S1, the mixed solution comprising rubidium, cesium and potassium is obtained by dissolving mixed alum comprising rubidium, cesium and potassium in deionized water.
3. The low cost simplified process according to claim 1, wherein in S1, the potassium removal method comprises: adding tartaric acid into the mixed solution containing rubidium, cesium and potassium, wherein the molar ratio of the tartaric acid to potassium in the mixed solution containing rubidium, cesium and potassium is 0.2-0.7, heating to 50-95 ℃, reacting for 1-3h, standing for 12-24h, cooling, recrystallizing, centrifugally separating to separate rubidium salt and cesium salt in a crystal form, and keeping potassium tartrate in the solution to obtain a potassium tartrate solution and rubidium cesium salt crystals with potassium content lower than 0.0035%.
4. The low cost simplified process according to claim 1, wherein in S1, the aluminum removal method comprises: dissolving rubidium cesium salt crystals in deionized water, adding barium hydroxide solution or calcium hydroxide solution, heating and stirring to react while controlling the pH at the reaction end point to be 6.5-8.5, and preserving heat for 10-60min after reaching the reaction end point to precipitate aluminum in the form of aluminum hydroxide; centrifugally separating the reaction mixture to obtain clear liquid and precipitate slag; and (3) performing precise filtration on the clear liquid to obtain purified rubidium cesium salt solution and filter residues.
5. The simplified low cost process according to claim 1, wherein in S2, the pH of the purified rubidium cesium salt solution is adjusted to alkaline prior to cesium extraction, and the purified rubidium cesium salt solution and the filter residue are obtained by fine filtration; cesium extraction is carried out on the causticized and purified cesium rubidium salt solution.
6. The simplified low cost process according to claim 5, wherein in S2, before cesium extraction, calcium hydroxide or barium hydroxide solution is added to the purified rubidium cesium salt solution, and the mixture is heated and stirred to react at 90-97 ℃, the reaction temperature is controlled to be equal to or higher than 13.0, and the temperature is maintained for 10-60min after reaching the reaction end point, so that cesium is completely dissolved in the aqueous phase as cesium hydroxide; precisely filtering to obtain causticized purified cesium rubidium salt solution and barium slag or calcium slag; cesium extraction is carried out on the causticized and purified cesium rubidium salt solution.
7. The low cost simplified process according to claim 5 or 6, wherein in S2, the cesium extraction method is: taking a mixed solvent of t-BAMBP, diethylbenzene and kerosene as an extracting agent, and carrying out cesium extraction on the causticized and purified cesium rubidium salt solution to obtain a cesium extraction organic phase and a cesium extraction residual liquid; washing the cesium extraction organic phase by using water or dilute alkali aqueous solution as a detergent to obtain a washing solution and a cesium extraction organic phase after washing; and (3) after washing, carrying out back extraction on the cesium extraction organic phase by taking ammonium carbonate or oxalic acid as a back extractant to obtain cesium back extraction liquid, carrying out precise filtration on the cesium back extraction liquid, sequentially carrying out evaporation concentration crystallization, drying, calcining, recrystallizing and drying to obtain the high-purity cesium carbonate.
8. The simplified low cost process according to claim 1, wherein in step S1, the removal rate of potassium and aluminum in the mixed solution containing rubidium, cesium and potassium is up to 99.9% or more; after the treatment of the step S2, the cesium removal rate in the purified rubidium cesium salt solution reaches more than 99.9 percent.
9. The low cost simplified process according to claim 1, wherein in step S3, the solubles in the cesium raffinate are RbOH and the remaining impurities are mainly trace Ba, fe, ca, mg metal ions; introducing high-purity carbon dioxide gas to enable impurity metal ions to generate carbonate precipitates, and performing precise filtration to obtain purified rubidium carbide liquid; evaporating, concentrating, crystallizing, drying, calcining, redissolving in deionized water, evaporating, concentrating, crystallizing again, and drying to obtain high-purity rubidium carbonate.
10. The low cost simplified process according to any one of claims 1 to 9, characterized in that in step S3, high purity CO is fed to the cesium raffinate 2 The pH is adjusted to 8-9; the fine filtration is microporous filtration of 0.08-0.15 mu m.
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| CN115725855A (en) * | 2022-11-09 | 2023-03-03 | 新疆有色金属研究所 | Method for preparing high-purity cesium salt and high-purity rubidium salt |
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